Alkylolamine salts of sulphonated compounds



Patented Apr. 7, 1931 H harem OFFICE JEAN GEORGES KERN, OF WALTHAM, MASSACHUSETTS, AND CHARLES J. BALL, OF WILMINGTON, DELAWARE, ASSIGNORS TO E. I. DU PON'I DE NEMOUBS & COMP 9E WILMNGTON, DELAWARE, A. COREOBA'IION .OF

ALKYLOLAMINE SALTS OF SULPHONATED COMPOUNDS E0 firawing. original application filed August a, 1927, Serial No. 210,714. Divided and. this application filed. March 21, 1930. Serial No. 437,939.

The acid product of the mixture of the sul- 4' This case is a division of our copending appliczation Serial No. 210,71t, filed August 4; 192

s This invention relates to alkylolamine salts of aliphatic acids both saturated and unsaturated and to the sulfonic acid derivatives of these acids and .more particularly to the ethanolamine salts of the higher fatty acids.

This invention has as 0b ects the preparation of soluble oils, solvents and detergents as well as of antiseptic soaps.

These objects are accomplished by making the salts of the bases known as alkylolamines or hydroxy-alkylamines, more particularly of the ethanolamines, by combination with the fatty acids mentioned above by any of the well known methods for the production of salts.

The bases used for our purpose ma be represented by the following general formula:

aliphatic radical, R and R represent hydrogen or an aliphatic radical or a hydroxy aliphatic radical or a poly hydroxy aliphatic radical. In making these new soluble oils we may proceed as follows:

The free fatty acids are combined directly with an organic base or a mixture of such bases. If the fatty acid is a solid the preparation. is aided by the application of heat. It is also possible to start from the glycerides of the fatty acids, i. e., olive oil, cottonseed oil, castor oil, linseed oil and the like by saponifying the glycerides by heating with the base to a high temperature. In this case we find that the reaction is complete when a sample of the mixture dissolves entirely in water. If water is present at the start this may be driven oif, the base not being volatile, until a concentrated product is left behind. When making these products by this method it is found that an excess of base is necessary to give the most satisfactory results.

When preparing the products obtained from the sulphonated fatty acids we may proceed as follows:

phonated unsaturated acid as obtained by the action of sulfuric acid on an unsaturated oil such as castor oil in the well known manner is freed of mineral acid by washing. It is then freed of water either by settling or by any other suitable means and then enough of the alkylolamine base is added at ordinarv temperature to neutralize the acidity of the sulfonic acid group or of both sulfonic acid and the carboxylic acid groups. The following examples will serve to illustrate our method of procedure, but it is to be understood that the invention is not to be limited thereby:

Example 1 2823. 7 parts of free oleic acid are mixed with 1490 parts of tri-etnanolamine Example 2 parts of oleic acid are mixed with parts of a mixture containing 75% trl-ethanolamine and 20% of di-ethanolamine.

The products resulting from this procedure are semi-solids, particularly water soluble and ready for use without further treatment. It is possible that the resultant material may be a compound of the base with the oleic acid but this has not been definitely established and is, in fact, immaterial to the success of 260 parts tri-ethanolamine 200 parts water. i

The above mixture is heated on the water bath for several hours. The saponification proceeds slowly and in order to make it complete within reasonable time it is of advantage to add an excess, for example 30% triethanolamine, above the quantity mentioned.

Example 5 284. so paras ofdstearic acid are melted. 113:6 the melt are S tr The resultant product on cooling is a solid, not very soluble in water but very soluble in alcohol. It acts as an excellent assistant in promoting solution.

Example 6 282 parts oleic acid 91 parts of aminoropane diol NH -CH IH-(IEh-OIEI 0H are heated together until completely mixed. The product is very soluble in alcohol. In water the solution is cloudy but becomes clear .on the addition of some excess base, 0. g. 15

0 Ewample 7' 282 parts oleic acid are caused to react as given in the above example with r 119 parts of methyl di-enthanolamine CH --N=(CHg-CHz )2 The soap obtained in this way has the property, when in alcoholic solution, of dissolvin mercuric oxide and giving a relatively stable product soluble 1n water. This is altogether a surprlslng result and lllustrates the use of these new soaps for pharmaceutical purposes.

Ewample 8 E'zmmple 9 2. 7 parts of a crude sulphonated oil mixture in the form of free acids are mixed with 1 part of a mixture of diand tri-ethanolamine.

The products of Examples 8 and 9 are entirely soluble in water. They are thick yellow oils presumably containing salts of the bases of the sulfonic acids but this point has not been definitely established and is immaterial to the success of the invention. The products formed in this way are quite satisfactory for ordinary purposes.

In dyeing Ponsol blue GD double paste, Schultz No. 842, on cotton yarn in the package machine, using 5% of color, -2 sodium hydroxide, 3% hydrosulfite, the addition of 1% of the product formed by combining 1 mole of sulfo-ricinoleic acid and 1 mole triethanolamine, containing di-ethanolamine, results in a brighter, more level dyeing.

Example 10 If a pure product is needed the operation may be carried out as follows:

378 parts of pure suIfo-ricinoleic acid prepared by the action of chloro-suifonic acid on pure ricinoleic acid are mixed with 149 parts of tri-ethanolamine.

In the above case the addition of a further molecular equivalent of base produces a more soluble oil. The reason may be that the extra quantity of base combines with the carboxyl group but again this point has not been determined.

In the above examples any one of the bases g ticularly as as defined by the general formula given above may be used either alone or in mixture. The fatty acids may also be varied through a wide range.

By the term alkylol, as used herein e w mean to include an alkyl radical in which one or more hydrogens are replaced b a hydroxyl group, an may be represented by the following:

We have found that these products, which are essentially organicsoaps possess a greater dissolving power or'dispersing power for organic substances than do ordinary soaps. They possess the detergent property of soaps without the high alkalinity characteristic of sodium or potassium salts of the fatty acids. These rbducts for these reasons have a distinct a vantage for many purposes and parassistants in dyeing, and those compounds which are derived from sulphonated castor oil by the process mentioned are in many ways superior to ordinary sulphonated oils. Their superiority is evidenced by the greater evenness of the shades developed, the better utilization of the color, and the greater brilliance of the dyeing.

When added to water the brin about solution or dispersion in so ne a orm as to appear a solution of insoluble organic bases such as amino-azo-benzene, para-nitro-benzene, azo-diphenylamine, benzene-azo-naphthalene-azo-phenol, Rosanthrene base, diethyl-para-amino-phenol-l :4 naphtho-quinone-mono-imide, 2 4 di-nitro-benzenel-azodi-ethylaniline, etc. It takes about 2 to 5 parts of the solvent for 1 part of the insoluble base. These solutions may be used very successfully for the purpose of dyeing fibers of esterified cellulose.

It has also been found that these soaps dissolve metallic hydroxides and oxides, for example, mercuric oxide, and this property indicates their probable value in pharmacology, for example, in the production of antiseptic soaps and the like.

As many apparently widely different embodiments of this invention may be made without departing from the spirit thereof, it is to be understood that we do not intend to limit ourselves to the specific embodiments thereof except as indicated in the appended claims. j

We claim:

1. A product resulting from the chemical combination of a substance from the group consisting of sulfo-ricinoleic acid, and the product formed by the sulphonation of castor oil, with an alkylolamine.

2. A product resulting from the chemical combination of a substance from the group consisting of sulfo-ricinoleic acid, and the product formed by the sulphonation of castor oil, with an ethanolamine.

3. A product resulting from-the chemical combination of a substance from the group consisting of sulfo-ricinoleic acid, and the product ormed by the sulphonation of castor oil, with at least one of the substances from the oup consisting of di-ethanolamine and tri-et anolamine.

4. A product resulting from the chemical combination of a substance from the group consisting of sulfo-ricinoleic acid, and the product formed by the sulphonation of castor oil, with a substance taken from the grou consisting of mono-ethanolamine, di-ethano amine, tri-ethanolamine and amino-propane 5. A product resulting from the chemical combination of a substancefrom the group consisting of sulfo-ricinoleic acid, and the product formed by the sulphonation of castor oil, with tri-ethanolamine;

6. A product resulting from the chemical combination of a substance from the group consisting of sulfo-ricinoleic acid, and the product formed by the sulphonation of castor oil, with an excess of tri-ethanolamine.

7. A product resulting from the chemical combination of a substance from the group consisting of sulfo-ricinoleic acid and the product formed by the sulphonation of castor oil with a compound having the following formula:

Alk-OH in which Alk represents an aliphatic or 11%- droxy aliphatic radical, while both R; and 2 represent a monovalent substance from the group consisting of hydrogen, aliphatic radi- 40 cals, and hydroxy aliphatlc radicals. 4

8. A product resulting from-the chemical combination of a substance from the group consisting of sulfo-ricinoleic acid and the product ormed by the sulphonation of castor oil with a mixture of diand tri-ethanolamines. t

9. A product resulting from the chemical combination of a substance from the group consisting of sulfo-ricinoleic acid and the product ormed by the sulphonation of castor oil with di-ethanolamine.

10. A product resulting from the chemical combmation of a substance from the group conslsting of sulfo-ricinoleic acid and the product ormed by the sulphonation of castor oil with mono-ethanolamine.

In testimony whereof we afiix our signatures. JEAN GEORGES KERN. CHARLES J. SALA. 

